CN1013659B - Method and facility for producing silicon nitride powder - Google Patents

Method and facility for producing silicon nitride powder

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Publication number
CN1013659B
CN1013659B CN 89106804 CN89106804A CN1013659B CN 1013659 B CN1013659 B CN 1013659B CN 89106804 CN89106804 CN 89106804 CN 89106804 A CN89106804 A CN 89106804A CN 1013659 B CN1013659 B CN 1013659B
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China
Prior art keywords
liquefied ammonia
silicon
continuously
organic solvent
imide
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CN 89106804
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Chinese (zh)
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CN1040559A (en
Inventor
张培志
毕玉惠
于政波
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Shan Dong Industrial Ceramic Research Inst Of National Building Material Indust
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Shan Dong Industrial Ceramic Research Inst Of National Building Material Indust
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Priority to CN 89106804 priority Critical patent/CN1013659B/en
Publication of CN1040559A publication Critical patent/CN1040559A/en
Publication of CN1013659B publication Critical patent/CN1013659B/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)

Abstract

The present invention relates to equipment for implementing a method for manufacturing silicon nitride. The method of the present invention comprises that in an organic solvent, SiCl4 reacts with liquid ammonia so that silicon imine is generated; then, the silicon imine is heated up so as to be decomposed into Si3N4 powder, wherein with the continuous feeding realized by a reaction vessel, a hydraulic spray scrubber, a hydraulic cyclone separator, a rotary kiln for thermal decomposition and crystallization and other devices, the Si3N4 powder is continuously produced. The product manufactured by the method of the present invention has the advantages of high purity, superfine size of the Si3N4 powder containing more than 96% of Si3N4, less than 1% of O, less than 10 PPM of C, less than 10 PPM of Cl-and less than 300 ppm of metallic impurities, particle size less than 0.5 mu m and yield reaching 97%.

Description

Method and facility for producing silicon nitride powder
The present invention relates to a kind of manufacture method and equipment of alpha-silicon nitride powders, be applicable to the preparation of metal nitride, product is used to prepare the nitride goods with superhard resistance toheat.It comprises the steps: that at first silicon tetrachloride and liquefied ammonia generate silicon imide in the organic solvent surface reaction, then the silicon imide thermolysis is made alpha-silicon nitride powders.
Disclose a kind of metal silicon nitride manufacturing method of power in the clear 56-44006 of Japanese Patent, its purpose is in order to solve remove and problem by product ammonium halide " smog " occluding device, pipeline of the reaction heat that metal halide and liquefied ammonia vigorous reaction are produced in the prior art.Its content is to have added organic solvent immiscible with it and that proportion is bigger than liquefied ammonia in the reactor of liquefied ammonia and metal halide, the reaction of metal halide and liquefied ammonia can carry out the reaction that generates silicon imide by realizing in the organic solvent layer that metal halide is passed into the reaction system bottom smoothly.Its weak point is that this method is a step reaction, can not serialization production, after every batch reaction is finished, need all shift away solvent and product, solvent load is very big, silicon imide being transferred in the electric furnace in the pyrolysated process, cause the oxygen level of product to raise in addition also easily by aquation, oxidation, organic solvent with separating of product the bad carbon content of product that also causes easily increase.
The objective of the invention is to avoid above-mentioned weak point of the prior art and a kind of manufacturing high pure and ultra-fine Si is provided 3N 4The continuous production method of powder reaches the C, the Cl that reduce in the product simultaneously -With the purpose of 0 foreign matter content such as grade, improve Si 3N 4The quality of powder reduces the consumption of organic solvent.
Purpose of the present invention can reach by following measure:
The present invention generates silicon imide with silicon tetrachloride and liquefied ammonia in the organic solvent surface reaction, is heated then and decomposes the method and apparatus that makes alpha-silicon nitride powders, it is characterized in that carrying out continuously as follows:
(a) silicon imide is synthetic: at first add liquefied ammonia and the immiscible with it and proportion organic solvent greater than liquefied ammonia in the reactor that agitator and multihole distributor are housed [2], feed in the organic solvent layer continuously silicon tetrachloride and rare gas element and constantly additional liquefied ammonia then, rare gas element carries silicon tetrachloride and evenly arrives organic solvent and liquefied ammonia interface by multihole distributor [8a], generate silicon imide and ammonium chloride with the liquefied ammonia reaction, float on above the organic solvent layer, reaction heat is absorbed as heat of gasification by liquefied ammonia and makes the gasification of part liquefied ammonia, the NH of generation 4Cl smog is also absorbed by liquefied ammonia, avoids pipe-line equipment to stop up, and reaction can continuously be carried out.
(b) washing of silicon imide: silicon imide that generates in reactor and byproduct ammonium chloride are flowed through by reactor outlet with the liquefied ammonia fluid spray scrubber [3] of liquefied ammonia nozzle [10] and porous filter plate [8b] are housed, in spray scrubber, silicon imide obtains washing, by product NH 4Cl is dissolved in the liquefied ammonia, by reclaiming behind the porous filter plate.The spray rate of liquefied ammonia can be regulated according to the speed that reaction is carried out, and guarantees the silicon imide washing fully.
(c) solid-liquid separation: the silicon imide after the spray scrubber washing flows into wet cyclone [4] with the liquefied ammonia fluid by the spray scrubber outlet, separates through spinning liquid, and silicon imide separates with liquefied ammonia, the liquefied ammonia recycling use, and silicon imide enters thermal decomposition furnace.
(d) thermolysis: the silicon imide from wet cyclone enters thermolysis crystallization processing stove [5] continuously, heats in inert gas atmosphere, successively enters arid zones, thermolysis band and crystallization band, makes α-Si at last 3N 4Powder, discharging continuously.
Purpose of the present invention can also reach by following concrete measure:
The organic solvent that silicon tetrachloride and liquefied ammonia reaction generate the required usefulness of silicon imide is aliphatic hydrocarbon or the aromatic hydrocarbon that contains 5～7 carbon atoms in the molecule, or any two or more mixture wherein, toluene is adopted in suggestion: hexanaphthene=1: 1, according to method of the present invention, organic solvent once adds and can use continuously, in the batch synthesis method described in the Japanese Patent JP5644006, every production 1 gram Si 3N 4Powder need consume the 33ml organic solvent.
Synthetic and the thermolysis of silicon imide all need be carried out in inert gas atmosphere, and nitrogen is adopted in suggestion.
The raw material silicon tetrachloride and the liquefied ammonia of synthetic silicon imide will feed in accordance with the appropriate ratio, and the ratio that suggestion is adopted is SiCl 4: NH 3=1: 10～20, preferably adopt 1: 10～15, can guarantee the SiCl that feeds like this 4Complete reaction can make reaction heat in time take away by product NH again 4Cl " smog " also can fully be absorbed, and guarantees the carrying out that reaction is continual and steady.
Multihole distributor in multihole distributor in the reactor [2] and the spray thrower [3] is made the most handy porous ceramic plate by metal, plastics, stupalith.
The installation site of multihole distributor [8a] is apart from reactor outlet lower edge 5～20cm, 3cm at least.The effect of this grid distributor is to make raw material SiCl 4Be diffused on the interface equably and react, simultaneously product and organic solvent are played buffer action, the silicon imide of generation is accumulated on grid distributor, surpass outlet and just flow in the spray scrubber.
The building-up reactions of silicon imide can be carried out under atmospheric low-temperature, also can add to depress at normal temperature and carry out, and considers that our suggestion of equipment manufacturing cost carries out under atmospheric low-temperature, and the temperature of reaction that suggestion is adopted is 0～-80 ℃, preferably-40～-55 ℃.
The main filtration of the screen plate of spray scrubber bottom, its setting angle α is 45 °～80 °, is preferably in 60 °～75 °.Product C l after the washing -Content is lower than 10PPM.
It is that continuous analysing silicon imines is made α-Si that the thermolysis crystallization is handled stove [5] 3N 4Key equipment, preferably adopt the rotary type stove and tilt to install, along with the rotation of tilting rotary kiln, silicon imide enters arid zones, thermolysis band and crystallization band in proper order, finally can obtain high-purity ultra-fine a-Si continuously 3N 4Powder.
The most outstanding feature of method of the present invention is by equipment continuously feeding of the present invention, and discharging has continuously realized Si 3N 4The serialization of powder production, thus the productive rate and the quality of product improved.
The related key equipment of method of the present invention is the reactor of band stirring and multihole distributor, spray-type washer, wet cyclone and tilting rotary furnace.
The drawing of accompanying drawing is described as follows:
Fig. 1, manufacturing Si 3N 4The processing unit synoptic diagram of powder.
1 anhydrous ammonia tank, 2 reactors, 3 spray scrubbers, 4 wet cyclones, 5 thermolysis crystallizations are handled stove, 6 liquefied ammonia, NH 4Cl withdrawing can, 7 thermolysis crystallization stove seal casinghousings, 8a multihole distributor, 8b porous filter plate, 9 agitators, 10 spray washing shower nozzles, 11a liquefied ammonia valve, 11b liquefied ammonia valve, 12N 2Air valve, 13SiCl 4, organic solvent adds valve, 14, blow-off valve, 15 vacuum valves, 16 reactor outlet valves, 17 liquefied ammonia fluid valves, 18N 2Air valve, 19 α-Si 3N 4Liquefied ammonia, NH after bleeder valve, 20 washings 4Cl recovery valve, 21 liquefied ammonia gasification recovery valve, 22 by product NH 4The interfacial layer of Cl bleeder valve, 23 organic solvents and liquefied ammonia, 24 liquefied ammonia, 25 organic solvents.
Fig. 2: the X-diffractogram of product.
Fig. 3: the stereoscan photograph of product.
The present invention will now be further detailed embodiment:
Embodiment 1:
Adopt fluorine Lyons or dry ice refrigeration means that reactor [2] is cooled to-50 ℃, the empty footpath of porous ceramics grid distributor is 1mm, and pore size distribution is 25 hole/inches, and grid distributor is from outlet lower edge 10cm.Shut-off valve [19], [20], [17], [18], [11a], [11b], [13], [12], [14], open valve [16], [15] vacuumize half an hour, shut-off valve [15] is then opened the logical N of valve [12] 2, three times so repeatedly, make total system become N 2Atmosphere.Shut-off valve [15], [16], [12] are opened [13] and added toluene: the mixed organic solvents of hexanaphthene=1: 1 is to 7cm place, porous plate pottery grid distributor upper end, and shut-off valve [13] is opened valve [11a] and put into liquefied ammonia to 30cm place, discharge port upper edge, opens valve [12] and leads to N 2Bubbling is opened valve [13] and is fed SiCl 4To reactor bottom, start agitator [9] simultaneously, SiCl 4Be diffused in the organic solvent, along with N 2Bubble agitate stirring with agitator, the SiCl in the solvent 4Upwards be diffused into interfacial layer equably by porous ceramics grid distributor [8a] and contact with liquefied ammonia and react, open valve [16], the silicon imide of generation flows in the spray scrubber [3] with the liquefied ammonia fluid, by product NH 4The Cl major part is dissolved in the liquefied ammonia liquid, and reaction generates heat and makes the gasification of part liquefied ammonia.So adjust SiCl 4And NH 3Throughput ratio at 10ml/min: 100ml/min, control mixing speed be 300 rev/mins, N 2The amount of blasting be 3l/min, make the reaction continual carrying out.Open valve [11b] and enable spray scrubber [3], liquefied ammonia makes the NH in the silicon imide by the silicon imide that the drip washing of spray scrubber nozzle generates 4Cl dissolves by the drip washing repeatedly of liquefied ammonia and is filled in the withdrawing can [6] by filter plate of porous ceramic [8b] with liquefied ammonia, silicon imide flows in the wet cyclone [4] after washing, separate through spinning liquid, liquid phase flows in the withdrawing can [6], the solid product silicon imide flows in the rotary kiln [5], opens the logical N of valve [8] 2, silicon imide is through 100～600 ℃ of dryings in low temperate zone, and 600～1200 ℃ of thermolysiss in temperate zone in entering enter 1200～1550 ℃ on crystallization band at last, begin after 5 hours to utilize the storage in vacuum mode to collect the Si of generation from discharge port [19] 3N 4Powder.The final product that generates is a white powder, through X-diffraction analysis α-Si 3N 4Content is 96%, β-Si 3N 4Be 4%, [Fig. 2]; The scanning electron microscope analysis product is for there being the spheroidal particle [Fig. 3] of reunion slightly, and sreen analysis shows; Particle＜0.5 μ m; Chemical analysis shows 0＜1%, Cl -＜10PPM, C＜10PPM, metal total impurities content Me＜300PPM.Productive rate reaches 97%.
Embodiment 2:
With embodiment 1 identical operation steps and order, with the temperature regulation to 0 of reactor ℃, organic solvent is selected hexanaphthene for use, and the pressure of keeping reactor is 4.5kg/cm 2, the angle [alpha] of regulating spray scrubber [3] is 70 ℃, the product that obtains at last is α-Si 3N 4Powder, performance, purity are identical with embodiment 1, and productive rate is 81%.
The present invention has following advantage than prior art:
1, can produce continuously.
2, organic solvent once adds, the long-term use.
3, improve the quality of products 0＜1%, Cl-＜10PPM, C＜10PPM, metal total impurities content＜300PPM.
4, improving productive rate reaches more than 97%.

Claims (6)

1, a kind ofly at first generate silicon imide in the organic solvent surface reaction, be heated then and decompose the method that makes alpha-silicon nitride powders, it is characterized in that carrying out continuously as follows by silicon tetrachloride and liquefied ammonia:
(a) synthetic continuously silicon imide: raw material silicon tetrachloride liquefied ammonia and rare gas element feed in the interior organic solvent layer of reactor continuously, and product silicon imide and by-product ammonium chloride float on above the organic solvent.
(b) silicon imide continuous washing: product silicon imide and by-product ammonium chloride are brought into spray scrubber continuously by the liquefied ammonia fluid, and silicon imide obtains washing, and chloride leach is recovered in liquefied ammonia continuously.
(c) silicon imide separates continuously with liquefied ammonia: the silicon imide after the washing enters wet cyclone with the liquefied ammonia fluid, and through spinning liquid separation continuously, silicon imide separates with liquefied ammonia.
(d) Continuous Heat is decomposed: silicon imide enters the thermolysis crystallization continuously and handles stove, progressively decomposes continuously in inert atmosphere and carries out crystallization, product α-Si 3N 4Discharging continuously.
2, a kind of being used for generates silicon imide by silicon tetrachloride and liquefied ammonia in the reaction of organic solvent liquid level, is heated then and decomposes the equipment that makes silicon nitride, and this equipment comprises reactor, the washing moisture eliminator, and stoving oven is characterized in that:
(a) in reactor lower part organic solvent liquid layer multihole distributor is housed, rare gas element carries silicon tetrachloride and evenly arrives organic solvent and liquefied ammonia interface by this multihole distributor, and with the liquefied ammonia reaction, product floats on the organic solvent upper strata, and reaction is carried out continuously;
(b) being sprayed on the reactor rear portion links to each other with outlet and adorns a spray scrubber that has liquefied ammonia nozzle and a porous filter plate; Be washed by contacting continuously with liquefied ammonia that top spray gets off from the effusive product silicon imide of reactor outlet, by-product ammonium chloride is dissolved in the liquefied ammonia by reclaiming behind the porous filter plate;
(c) link to each other and adorn a wet cyclone with outlet at the spray scrubber rear portion, so that the separation of silicon liquefied ammonia;
(d) behind wet cyclone, link to each other and adorn thermolysis crystallization processing stove with outlet; Silicon imide enters this continuously and handles stove in inert gas atmosphere, and one-time continuous thermolysis and crystallization are constantly emitted finished product.
3,, it is characterized in that described multihole distributor and porous filter plate made by metal, plastics, stupalith according to the equipment of claim 2.
4,, it is characterized in that described multihole distributor installation site is apart from reactor outlet lower edge 5～20cm according to the equipment of claim 2.
5, according to the equipment of claim 2, the setting angle α that it is characterized in that described spray scrubber bottom porous filter plate is 45 °～80 °.
6,, it is characterized in that it is the rotary type stove that described thermolysis crystallization is handled stove according to the equipment of claim 2.
CN 89106804 1989-08-24 1989-08-24 Method and facility for producing silicon nitride powder Expired CN1013659B (en)

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CN1013659B true CN1013659B (en) 1991-08-28

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Families Citing this family (16)

* Cited by examiner, † Cited by third party
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DE3924361A1 (en) * 1989-07-22 1991-01-24 Huels Chemische Werke Ag METHOD FOR PRODUCING SILICON DIIMIDE WITH A LOW CARBON CONTENT
CN1064024C (en) * 1997-11-20 2001-04-04 浙江大学 Method and apparatus for production of high purity ultrafine silicon nitride
CN104925764B (en) * 2015-06-12 2017-07-07 常州汉耀复合材料有限公司 The device of silicon imide serialization generation
CN106367733B (en) * 2015-07-24 2019-02-22 东莞市中镓半导体科技有限公司 A kind of device and method for removing HVPE equipment pipe tail gas deposit
CN105217583B (en) * 2015-09-28 2017-05-31 青岛桥海陶瓷新材料科技有限公司 A kind of method for preparing nanoscale high purity silicon nitride
CN106672922B (en) * 2015-11-11 2019-01-22 新疆晶硕新材料有限公司 A kind of system producing silicon nitride
CN108394876B (en) * 2017-02-07 2021-04-02 新疆晶硕新材料有限公司 Nitrogen silane and production method thereof, silicon nitride and production method thereof
CN108928806B (en) * 2017-05-25 2020-08-04 新疆晶硕新材料有限公司 Method for synthesizing silicon imine and silicon imine
CN109384206B (en) * 2017-08-09 2020-07-17 新疆晶硕新材料有限公司 Production device and production method of silicon imine, production system and production method of silicon nitride
CN107557866A (en) * 2017-08-28 2018-01-09 青岛桥海陶瓷新材料科技有限公司 The preparation method of silicon nitride crystal whisker
CN107954723B (en) * 2017-12-19 2020-11-10 清华大学 Preparation method of alpha-phase silicon nitride powder
CN109608205B (en) * 2019-02-02 2021-04-16 清华大学 Method for preparing equiaxed alpha-phase silicon nitride powder
EP3950583B1 (en) * 2019-03-29 2024-04-17 Denka Company Limited Silicon nitride powder and method for producing same, and method for producing silicon nitride sintered body
CN113148966B (en) * 2021-04-20 2022-04-29 安徽工业大学 Method for preparing high-purity silicon nitride powder by ammonolysis method
CN115106031A (en) * 2022-05-21 2022-09-27 倪磊 Fluorine-silicon separation equipment for fluorine-silicon mixture
CN115337882A (en) * 2022-08-31 2022-11-15 南京延长反应技术研究院有限公司 Reaction system and method for producing silicon nitride

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